Physics
Scientific paper
Jun 2010
adsabs.harvard.edu/cgi-bin/nph-data_query?bibcode=2010mss..confeti11m&link_type=abstract
"International Symposium On Molecular Spectroscopy, 65th Meeting, Held 21-25 June, 2010 at Ohio State University. http://molspec
Physics
Theory
Scientific paper
The similarities of Rayleigh-Schrödinger (RSPT) and Van Vleck (VVPT) perturbation theories are discussed. It is shown that a straightforward application of RSPT produces the VVPT Hamiltonian at the highest order of the contact transformations applied, which is always a diagonal matrix. VVPT Hamiltonians at an order higher than this are non-diagonal, but it is shown that a careful application of RSPT can produce the same matrices. The usefulness of these higher-order ``dressed" Hamiltonians in treating resonance is discussed, as well as specific discussions of first-order Fermi, second-order Darlington-Dennison, and higher-order resonances. Lastly, VVPT is discussed in a wavefunction-based context and RSPT in a Hamiltonian-based context, and the approaches are contrasted.
Matthews D. A.
Stanton John F.
Vázquez Juana
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